Method of forming a conductive image using high speed electroless plating

ABSTRACT

A method of producing a conductive image using high speed electroless plating according to the present invention preferably includes the steps of: preparing the surface of a substrate; depositing a metal coordination complex into the surface of the substrate; reducing the metal coordination complex to form an image in the surface of the substrate; depositing a protective material onto the image; electrolessly plating metal onto the image.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/453,559, filed Aug. 6, 2014, which is based on U.S. ProvisionalApplication No. 61/862,924, filed Aug. 6, 2013, the entire contents anddisclosure of which are herein incorporated by reference.

BACKGROUND OF THE INVENTION

This invention relates to a high speed electroless plating solution, amethod of producing the same with specific focus on the field ofelectronics.

In the manufacturing of electronic devices the degree of densityincreases and the size of the traces and spaces between the trace linedecreases, all of which must be formed on a substrate. As the density ofthe trace line increases, the net resistance of the conductive materialis substantially increased overall. The increase in resistance in theconductive traces of electronic devices causes the quality of thedevices to deteriorate due to signal delay. Therefore, it is desirableto decrease the resistance of plated conductive trace line.

Copper as a conductive material has relatively low specific resistanceand excellent electro-migration resistance. When copper is specified forthe conductive material set within an electronic device, it is preferredthat current capacity will remain unaffected relative to theminiaturization and high integration density of the smaller devices,that is now desirable. Electroless plating is a method of plating aconductive material or metal by the reaction of reducing and oxidizingin solution to provide the conductive material or metal on the surfaceof an activated or pretreated substrate. By using the electrolessplating method of plating, the metal is uniformly and simultaneouslydeposited throughout the entire substrate. Electroless plating does notuse an external power source (as does electrolytic plating), in whichhomogeneity of plating is enhanced.

Commonly, an electroless copper plating solution contains a source ofcupric ions, a complexing agent for cupric ions, a reductant for cupricions, and a pH adjusting agent. When copper plating was performed usingthe electroless copper plating solution, obtaining a plating film havinghigh adhesion was difficult, the speed of forming a metal plating filmwas low, and uniform plating of the entire substrate was difficult.

Additionally, the electroless copper plating solution could contain astabilizer(s) for improving the stability of the plating bath, asurfactant for improving the properties of the plating film, along withvarious additives which can be added to the electroless copper platingsolution, so as to improve the stability and material properties of theplating solution and the characteristics of the copper image (pattern)designed. However, conventional electroless copper plating solutionshave provided a copper deposition that displays both sufficiently lowelectrical resistance and excellent bonding. The simple mechanism of theelectroless copper plating solution is when a reducing agent in solutioncauses an oxidation reaction with a catalytic action of copper.

To briefly explain the mechanism of the electroless copper plating, thereducing agent in the plating bath causes an oxidation reaction with acatalytic action of copper, which releases electrons. Consequently, thecupric ion is reduced by receiving the released electrons, anddepositing a copper plating on the substrate in the solution.

In the plating industry, practically all of the electroless coppersolutions/baths utilized formaldehyde as a reducing agent.Unfortunately, formaldehyde is a toxic chemistry and a carcinogen, andis not environmentally favorable in the electronic industry. Withrespect to formaldehyde as an issue, it has been suggested to useglyoxylic acid instead of formaldehyde in the electroless copper platingsolution/bath. However, the oxidation reaction of glyoxylic acid isslower, and it is probably caused by the catalytic action of copper.Glyoxylic acid releases fewer electrons from the oxidation reaction, andconsequently the plating reaction ensues slower in the electrolesscopper plating solution/bath using glyoxylic acid as the reducing agent.The objective of which was to provide an electroless copper platingsolution/bath that would be less toxic and more consistently stable inproduction.

Predominantly, the normal electroless copper plating solution/bath usesa solution containing ethylenediamine tetraacetate (EDTA) as acomplexing agent. EDTA is also slow in the deposition rate of thecopper, so that it is essential to increase the speed of the depositionrate of the electroless copper. Since the time required for the platingis longer, then the production efficiency is lowered, which causes achallenge to overcome, or the need for a high speed electroless coppersolution/bath.

As the electronic device dimensions are manufactured smaller andsmaller, the aspect ratio of vias and 3D features (such as trenches) aredesigned with higher density and narrower traces and spaces (line widthand space), processes will need to be developed to feed the drive of thedesigners. Conventional processes for depositing copper into thesefeatures include physical vapor deposition (PVD), chemical vapordeposition (CVD), atomic layer deposition (ALD), and electroplating.These processes have their innate challenges that electroless platingcan overcome. Electroless copper plating holds great promise as a methodto form a copper trace or line for Ultra large Scale Integration (ULSI),and as a replacement for the sputtering, vapor deposition andelectrolytic copper plating systems presently employed.

It is a purpose of this innovation to solve the above mentionedchallenges of the conventional techniques and to offer a practice or asystem for electroless plating capable of improving the deposition andacceleration of the electroless plating solutions/baths.

An additive process is needed for printed circuit board fabrication thathas all of the benefits of other additive processes but which displaysenhanced bonding characteristic with substrates. The current inventionprovides such an additive process.

SUMMARY OF THE INVENTION

A method of forming a conductive image using high speed electrolessplating is described herein that overcomes the limitations noted above.

A method of conductive image using high speed electroless platingaccording to the present invention preferably includes the steps of:preparing the surface of a substrate; depositing a metal coordinationcomplex into the surface of the substrate; reducing the metalcoordination complex to form an image in the surface of the substrate;depositing a protective material onto the image; electrolessly platingmetal onto the image. Accordingly, electroless plating may beaccomplished at a high speed and efficacy.

Various features and advantages of the present invention will becomeapparent from the following more detailed description, taken inconjunction with the accompanying drawings, which illustrate, by way ofexample, the principles of the presently described process and itsresultant product.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

Illustrated in the accompanying drawing(s) is at least one of the bestmode embodiments of the present invention In such drawing(s):

FIG. 1 is an illustrative flow-chart of an exemplary method inaccordance with at least one embodiment of the present invention;

FIG. 2 illustrates an exemplary bonding in the surface of the substratein accordance with at least one embodiment of the present invention; and

FIG. 3 illustrates exemplary tuned magnetic field states (FIGS. 3A to3D) in accordance with at least one embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The above described drawing figures illustrate the described inventionin at least one of its preferred, best mode embodiments, which isfurther defined in detail in the following description. Those havingordinary skill in the art may be able to make alterations andmodifications to what is described herein without departing from itsspirit and scope. While this invention is susceptible of embodiment inmany different forms, there is shown in the drawings and will herein bedescribed in detail a preferred embodiment of the invention with theunderstanding that the present disclosure is to be considered as anexemplification of the principles of the invention and is not intendedto limit the broad aspect of the invention to the embodimentillustrated. Therefore, it should be understood that what is illustratedis set forth only for the purposes of example and should not be taken asa limitation on the scope of the present apparatus and its method ofuse.

As shown in FIG. 1, in at least one embodiment, a method for forming aconductive image using high speed electroless plating comprises thesteps of: preparing the surface of a substrate; depositing a metalcoordination complex into the surface of the substrate; reducing themetal coordination complex to form an image in the surface of thesubstrate; depositing a protective material onto the image;electrolessly plating metal onto the image. As used herein, a“conductive image” refers to an electrically conductive surface pattern,for example and without limitation, that of a printed circuit.

Preparing the Substrate (Step 100)

As shown in FIG. 1, at least a portion of the substrate surface isprepared to be electrolessly plated with metal in accordance with Step100.

As shown in FIG. 2, according to at least one embodiment, a substrate 10having a surface 20 with a thickness 22 is provided and at least aportion of the substrate surface is prepared to be electrolessly platedwith metal. As used herein, the term “at least a portion of thesubstrate surface” refers to the entire substrate surface or any portionthereof. Preferably, the substrate is a non-conductive substrate suchas, for example, glass, silicone or polymer. In at least one embodiment,preparing the substrate surface to be electrolessly plated with metalincludes at least one of: pretreating the portion the substrate surface,and activating the portion of the substrate surface.

Returning to FIG. 1, in at least some embodiments, the step of preparingthe substrate surface includes pre-treating the portion of the substratesurface, i.e. removing unwanted material from the portion of thesubstrate surface whose presence during the process of the instantinvention may result in poor plating. Pretreatment of the substratesurface may be accomplished according to known methods in the art.

In at least some embodiments, the step of preparing the portion of thesubstrate surface includes activating the portion of the substratesurface, i.e. rendering the substrate surface more amenable tointeraction with and subsequent physical or chemical bonding to anothermaterial that is disposed onto the surface of the substrate. Activatingthe substrate surface may comprise altering the topography of thesubstrate surface and/or rendering the substrate surface more diffusiveto incident electromagnetic radiation.

In at least one embodiment, activating the substrate surface comprisesaltering the topography of the substrate surface. The topography of thesurface can be altered by any means known in the art or hereinafterdeveloped, including mechanical, chemical, plasma, laser or acombination thereof. In at least one embodiment, the topography of thesubstrate surface may be altered via etching, including mechanical,chemical, plasma or laser etching.

Mechanically altering the substrate surface topology includes, forexample, molding the substrate with the desired topology. In suchembodiments, molten substrate material may be deposited into a mold thatimparts the desired surface topology to the produced substrate.

Chemically altering the substrate surface topology includes, forexample, acid etching, base etching, oxidative etching and plasmaetching. Acid etching refers to the use of a strong acid to alter thesurface properties of the surface of the substrate, typically glass, andis known in the art. Base etching refers to the use of a basic substanceto alter the topology of the surface of the substrate, typically organicpolymers, and is known in the art. Oxidative etching refers to the useof a strong oxidant to alter the surface properties of the surface ofthe substrate, and is known in the art.

Altering the substrate surface topology using plasma includes, forexample, plasma etching. Plasma etching refers to the process ofimpacting the surface of a substrate with a high-speed stream of a glowdischarge of an appropriate gas, and is known in the art.

Altering the substrate surface topology using laser includes, forexample, laser etching. Laser etching refers to the process of directinga laser beam at the substrate surface so as to remove material from thesubstrate surface.

In at least one embodiment, the topography of the substrate surface maybe altered in the form of a predetermined pattern or designedtopography. As discussed further herein, the predetermined pattern mayform a trace for the image formed in the substrate surface. This isparticularly applicable where laser etching is used to prepare thesubstrate surface.

In at least one embodiment, activating the substrate surface comprisesrendering the substrate surface more diffusive, i.e. permeable toanother material that is disposed into the surface of the substrate. Insuch embodiments, the surface of the substrate may be exposed to a fluidthat softens and/or swells the substrate surface, permitting materialapplied to the surface to physically interact within the surface (i.e.within the surface thickness), and resulting in the material being moretightly bonded to the substrate surface—particularly when dried.

Depositing the Metal Coordination Complex (Step 200)

As shown in FIG. 1, a metal coordination complex is deposited into thesurface of the portion of the substrate surface in accordance with Step200.

According to at least one embodiment, a metal coordination complex isprovided for deposition into (i.e. within the thickness of) thesubstrate surface. As used herein, the term “metal coordination complex”refers to those metal complexes understood by those of skill in the artto have the desired properties described herein. Preferably, the metalcoordination complex is a para-magnetic or ferro-magnetic metalcoordination complex. An exemplary metal coordination complex isdescribed, for example, in U.S. Pat. No. 8,784,952 and U.S. Pat. No.8,784,953, the entire contents and disclosures of which are hereinincorporated by reference.

In at least one embodiment, the metal coordination complex is aferromagnetic coordination complex, including iron, nickel or cobalt,preferably iron. In at least one embodiment, the metal coordinationcomplex is a paramagnetic coordination complex, including tungsten,cesium, aluminum, lithium, magnesium, molybdenum, tantalum, preferablyaluminum or molybdenum. In at least one embodiment, the metalcoordination complex is a nobel metal complex, including ruthenium,rhodium, palladium, osmium, iridium, platinum, silver, copper or gold,preferably palladium or platinum. In at least one embodiment, the metalcoordination complex is a combined coordination complex comprising atleast one of the ferromagnetic, paramagnetic and nobel metal coordinatedcomplexes discussed above.

In at least one embodiment, the step of depositing the metalcoordination complex into the substrate surface comprises the sub-stepsof: depositing the metal coordination complex onto the substratesurface; applying a magnetic field to the metal coordination complex soas to cause the ligands of the metal coordination complex to align andbe drawn into the thickness of the substrate surface; tuning themagnetic field such that the ligands of the metal coordination complexare more aligned and more deeply drawn into the thickness of thesubstrate surface; and removing the magnetic field. In accordance withat least one embodiment, these sub-steps may be performed in any order,except that the step of removing the magnetic field preferably occursafter the metal coordination complex is applied to the surface of thesubstrate under the influence of the applied magnetic field.

In at least one embodiment, the magnetic field is applied by placing thesubstrate surface on or near a source of the magnetic field. Preferably,the magnetic field is orthogonal to the substrate surface. The magneticfield may be generated, for example, by one or more permanent magnets,electromagnets, or any combination thereof. Preferably, the fieldstrength of the magnet is at least 1000 Gauss, and more preferably, isat least 2000 Gauss. Preferably, the magnet is a neodymium magnet. Themagnet also has preferred dimensions such that the portion of thesubstrate surface is entirely contained within the dimensions of themagnet. In some embodiments, the magnetic field is substantiallyorthogonal to the portion of the substrate surface at all intersectingpoints and/or has a substantially uniform flux density. Preferably, thesubstrate and the magnet are positioned such that the substrate surfaceis not separated from the magnet by the remainder of the substrate, butis the closest part of the substrate to the magnet—although alternativeconfigurations are contemplated.

In at least one embodiment, the magnetic field is a tunable magneticfield. In other words, the magnetic field flux density and structure isadjustable or tunable. In at least one embodiment, the metalcoordination complex is reactive to the applied magnetic field, and inparticular, to the structure (e.g. magnetic field flux density) of themagnetic field. Preferably, application of the tuned magnetic fieldcauses the metal coordination complex to align according to the magneticfield structure (e.g. flux density). In at least one embodiment, thestructure of the magnetic field may be selected based on, at leastpartially, the actual and/or desired structural alignment, shape,polarity and/or depth of the metal coordination complex within thesubstrate surface.

FIG. 3 illustrates exemplary tuned states of the magnetic field. Asshown in FIGS. 3A and 3D, for example, the magnetic field may beadjusted between various tuned states. FIGS. 3A and 3B, for example,illustrate elliptical magnetic fields in flattened (FIG. 3A) and rounded(FIG. 3B) configurations, according to at least one embodiment. Thedifferent tuned states apply different magnetic forces (both inmagnitude and direction) on the metal coordination complex, asillustrated by the magnetic field lines in FIG. 3. Accordingly, andbased upon the characteristics of the metal coordination complex,increasing the amplitude and power within the electromagnetic fieldforce electrons of the metal coordination complex to higher valencelevels of bonding. To this effect, the magnetic field may be tuned tovary (e.g. make greater) the applied magnetic force, which in turnvaries (e.g. makes stronger) bonding within the substrate surface.

In at least one embodiment, depending upon the molecule structure andpolarity of the metal coordinated complex, each field state may generatedifferent tangent sites within the substrate surface to share electrons,causing three different energy level bonding. Thus, tuning the magneticfield may comprise combining different electromagnetic field structureswith different energy levels. For example, as shown in FIGS. 3C and 3D,a Halbach Array or Alternating Polarity array may be utilized to effectthe advantages of the present invention according to at least oneembodiment.

It should be noted, however, that the exemplary magnetic fieldstructures described herein are provided for illustrative purposes, andall conceivable magnetic field structures. Moreover, as discussed above,the state of the tuned magnetic field may be selected according to thedesired metal image to be formed. For example, if it were desired toelectrolessly plate the entire substrate surface for the purpose of asemi-additive thin layer of plating, then the magnetic field may betuned to reflect a more horizontal, flat, elliptical shape with a highlevel of power (or Gauss). However, if, for example, it were desired toelectrolessly plate high density, fine features, then the magnetic fieldmay be tuned to set the coordination complex molecular structure andalignment such that the plating would build up vertically, limiting sidewall growth.

Without being held to any particular theory, it is believed that themetal coordination complex, under the influence of the magnetic field,will be drawn in toward the source of the magnetic field and thereby bemore deeply injected into the substrate surface. Additionally, or in thealternative, the magnetic field may cause the ligands of the metalcoordination complex to align in the direction of the magnetic field.Such alignment may further draw the ligands into the thickness of thesubstrate surface. A combination of the two processes may also occur.The result in any case is that the metal coordination complex is moretightly bound within the substrate surface than which would occurwithout the influence of the magnetic field.

In at least one embodiment, for substrate material commonly use in theelectronics industry (e.g. glass, etc.), the metal coordination complexpenetrates the thickness of the substrate surface in excess of a depthof 10%. In at least one embodiment, for substrate material commonly usein the electronics industry (e.g. glass, etc.), the metal coordinationcomplex penetrates the thickness of the substrate surface in excess of adepth of 15%. In at least one embodiment, for substrate materialcommonly use in the electronics industry (e.g. glass, etc.), the metalcoordination complex penetrates the thickness of the substrate surfacein excess of a depth of 20%.

In at least one embodiment, after the metal coordination complex isapplied to the surface of the substrate under the influence of theapplied magnetic field, the source of the magnetic field is removed.

In at least one embodiment, the metal coordination complex may bedeposited on the portion of the substrate surface via painting,spraying, roller applicator, or any other procedures known in the art orhereinafter developed. According to at least one embodiment, the metalcoordination complex may be deposited on the portion of the substratesurface by inkjet printing.

In at least one embodiment, the metal coordination complex may bedeposited on the portion of the substrate in accordance with the imageto be formed in the substrate surface. For example, a mask may be usedto deposit the metal coordination complex in accordance with the imageto be formed. Accordingly, in some embodiments, the metal coordinationcomplex is applied to the predetermined pattern formed in the substratesurface.

In at least one embodiment, the image comprises an electronic circuitdesign. Preferably, the electronic circuit is selected from the groupconsisting of an analog circuit, a digital circuit, a mixed-signalcircuit and an RF circuit. Accordingly, at least one embodiment may bepracticed to fabricate one or more of: analog circuits, digitalcircuits, mixed signal circuits, and RF circuits.

Forming the Image in the Surface of the Substrate (Step 300)

As shown in FIG. 1, an image is formed in the surface of the portion ofthe substrate surface in accordance with Step 300. The image is a metalimage formed of the metal coordination complex deposited within thesubstrate surface reduced to a zero oxidation state metal. An exemplaryreducing agent and reduction process is described, for example, in U.S.Pat. No. 8,784,952 and U.S. Pat. No. 8,784,953, the entire contents anddisclosures of which are herein incorporated by reference.

In at least one embodiment, the step of forming an image in the surfaceof the substrate comprises the following sub-steps: exposing thedeposited metal coordination complex to electromagnetic radiationaccording to the image to be formed; removing the unexposed metalcoordination complex so as to leave the metal image; and drying thesubstrate surface.

In at least one embodiment, the step of exposing the deposited metalcoordination complex to electromagnetic radiation includes exposing thedeposited metal coordination complex to at least one of: microwaveradiation, infrared radiation, visible light radiation, ultravioletradiation, X-ray radiation or gamma radiation. In some embodiments, thecomposition of the metal coordination complex may be such that the metalcoordination complex is sensitive to a particular range of theelectromagnetic spectrum. In addition, or alternatively, one or moresensitizers may be added to the metal coordination complex inassociation with it being disposed on the substrate, rendering thecoordination complex photosensitive or, if the complex is inherentlyphotosensitive, to render it even more so.

Exposure of the deposited metal coordination complex to electromagneticradiation reduces the metal coordination complex to a zero oxidationstate metal by activating the metal coordination complex toward areducing agent. Exposure to radiation renders the exposed portion of themetal coordination complex susceptible to reduction. The reducing agentreduces the metal coordination complex to elemental metal. The reducingagent may be any metal-inclusive salt where the metal has a reductionpotential that is greater, i.e., conventionally has a more negativereduction potential than the metal of the metal coordination complex.The result is that the exposed metal coordination complex is reduced toelemental metal according to the metal image.

In at least one embodiment, the step of removing unexposed (i.e.unreduced) metal coordination complex from the substrate surfacecomprises washing the surface with a solvent. The elemental metal imageresulting from the exposure (i.e. reduction) step is preferablyinsoluble in most solvents. Thus, washing the surface of the substratewith an appropriate solvent, which is determined by the composition ofthe initial metal coordination complex, will remove unexposed complexleaving the metal image. The metal image may be evenly dispersed overthe surface of the substrate if the surface of the substrate wasgenerally exposed, or the metal image may form a discrete pattern if thesubstrate surface was exposed according to such.

In at least one embodiment, once the unexposed metal coordinationcomplex is removed, the substrate is dried to complete formation of themetal image. In at least one embodiment, the step of drying the surfacecomprises drying at ambient or elevated temperature, preferably, using avacuum chamber.

The metal image can then be plated with another metal or coated with anon-metallic conductive material.

Depositing the Protective Material onto the Image (Step 400)

In advance of plating the metal image, a protective layer is preferablyapplied to the metal image (Step 400). This protective layer ispreferably a conductive material. In at least some embodiments, theprotective layer is a metal or conductive polymer that is applied by atleast one of: flash deposit, vapor deposition, electrostatic bonding, orthe like, all known in the art.

Electroless Plating Metal onto the Image (Step 500)

As shown in FIG. 1, the protected elemental metal image is subjected toan electroless plating process in accordance with Step 500. In thismanner a conductive metal layer is formed on the regions of theelemental metal image, resulting in a raised conductive surface. In atleast one embodiment, depositing the conductive metal layer onto thesubstrate surface comprises an accelerated electroless deposition ofmetal onto the portion of the substrate surface, and/or the metal imagecomprising the reduced metal coordination complex.

In at least one embodiment, the raised conductive surface comprises anelectronic circuit. Preferably, the electronic circuit is selected fromthe group consisting of an analog circuit, a digital circuit, amixed-signal circuit and an RF circuit. Accordingly, at least oneembodiment may be practiced to fabricate one or more of: analogcircuits, digital circuits, mixed signal circuits, and RF circuits.

In at least one embodiment, electroless plating of the metal image isaccomplished by applying to the substrate surface a solution of a saltof the metal to be deposited in the presence of a complexing agent (i.e.a complexed metal salt solution). Application of the complexed metalsalt solution to the substrate surface may be by brushing, spraying,submerging or any other application process known in the art orhereinafter developed. An aqueous solution of a reducing agent may besimultaneously or consecutively to the substrate surface having theapplied complexed metal salt solution. The metal complex is then reducedto afford elemental metal which adheres to the metal image already onthe surface of the substrate—i.e. an electrolessly deposited layer ofmetal on metal results.

Preferably, the complexing agent keeps the metal ions in solution andacts to stabilize the solution, generally. The complexed metal saltsolution and the reducing solution may be concurrently sprayed onto thepatterned substrate either from separate spray units, the spray streamsbeing directed so as to intersect at or near the substrate surface, orfrom a single spray unit having separate reservoirs and spray tiporifices, the two streams being mixed as they emerge from the spray tipand impinge on the substrate surface.

In at least one embodiment, electrolessly depositing the conductivemetal layer onto the portion of the substrate surface comprising thereduced metal coordination complex comprises applying to at least theportion of the substrate surface comprising the metal coordinationcomplex with a solution comprising a salt of the metal, a complexingagent and a reducing agent.

In at least one embodiment, electrolessly depositing the conductivemetal layer onto the portion of the substrate surface comprises applyingan electroless plating bath. The electroless plating solution/bathpreferably includes: a pretreating/cleaning/etching solution forelectroless plating comprising an alkali solution, a reducing agent anda completing agent; and a solution/bath of an electroless platingchemistry comprising a pH adjusting agent, a reducing agent, a metal ionand a completing agent.

In at least one embodiment, the pH adjusting agent is preferablyselected from the group comprising: KOH, NaOH, Ca(OH).sub.2, NH.sub4 OH(with a hydrogen ion concentration (pH) of 10.5 to 14) or the like.

In at least one embodiment, the reducing agent is preferably selectedfrom the group comprising: an aldehyde, hypophoshites (sodium orpotassium), hydrogen borate, hydrazine, glyoxylic acid, dimethylamineborane (DMAB), borohydride, cobalt (II) ethylenediamine complex, (in aconcentration of 2 to 8 percent mol/l) or the like.

In at least one embodiment, an accelerator may also be used, and ispreferably selected from the group comprising: carboxylic acid, glycolicacid, acetic acid, glycine, oxalic acid, succinic acid, malic acid,malonic acid, citric acid, phosphinic acid and nitrilotriacetic acid (ina concentration of 1 to 20 percent mol/l) or the like.

In at least one embodiment, the complexing agent is preferably selectedfrom the group comprising: EDTA, HEDTA, Rochelle salt, an organic acid,citric acid, tartaric acid, ammonium citrate, TEA, ethylene diamine,trialkyl monoamine, sodium potassium tartrate, triisopropanolamine, (ina concentration of 2 to 10 percent mol/l) or the like.

In at least one embodiment, the metal ion is a copper ion of coppercompounds preferably selected from the group comprising: CuSO.sub.45H.sub.2O, CuO, CuCl.sub.2, Cu(NO.sub.3).sub.2, (in a concentration of 1to 5 percent mol/l).

In at least one embodiment, the step of subjecting the substrate to anelectroless plating process comprises agitating the plating solution(i.e. plating bath). Preferably, agitation includes nitrogen agitationfor approximately 20 to 120 minutes, according to known methods in theart.

In at least one embodiment, the step of subjecting the substrate to anelectroless plating process comprises filtering the plating solution(i.e. plating bath). This is preferably performed with a less than 1micron filter, according to known methods in the art.

In at least one embodiment, the plating bath contains dissolved metalsalts of the metal to be plated as well as other ions that render theelectrolyte (i.e. metal salt) conductive.

When power is applied to the plating bath, including the submergedsubstrate surface portion, the metallic anode is oxidized to producecations of the metal to be deposited and the positively charged cationsmigrate to the cathode, i.e., the metal image on the substrate surface,where they are reduced to the zero valence state metal and are depositedon the surface.

In an embodiment of this invention, a solution of cations of the metalto be deposited can be prepared and the solution can be sprayed onto themetalized construct.

The conductive material to be coated on the elemental metal image mayalso comprise a non-metallic conductive substance such as, withoutlimitation, carbon or a conductive polymer. Such materials may bedeposited on the metal image by techniques such as, without limitation,electrostatic powder coating and electrostatic dispersion coating, whichmay be conducted as a wet (from solvent) or dry process. The process maybe carried out by electrostatically charging the metal image and thencontacting the image with nano- or micro-sized particles that have beenelectrostatically charged with the opposite charge to that applied tothe metal image. In addition, to further ensure that only the metalimage is coated, the non-conductive substrate may be grounded toeliminate any possibility of an attractive charge developing on thesubstrate or the substrate may be charged with the same polarity chargeas the substance to be deposited such that the substance is repelled bythe substrate.

EXAMPLE

An exemplary embodiment will now be described for illustration.

For the purpose of showing detailed information and design, the highspeed electroless process will focus upon copper to be deposited at ahigher rate than the industry norm, which is 1μ-3μ per hour, dependingupon the electroless copper chemistries available on the market, andavailable. Electroless copper plating has been catalyzed, in the past,by an active palladium surface, and continues to depositauto-catalytically on the newly reduced copper deposited. The depositionrate depends upon the half-reaction activity of the cupric ion reductionand formaldehyde oxidation on the active palladium and copper surfaces.The complexing agents can change the behavior of the half-reactions bystabilizing the cupric ion through complexation and by surfaceadsorption. Let's examine the complexing agents,ethylenediaminetetraacetic acid and triethanolamine (for example) on theelectrochemical reduction of cupric ions and the oxidation offormaldehyde (as the reducing agent). It can also be asserted thatchange in pH will accelerate the deposition rate of the electrolesscopper. The pH of the solution influences the reduction potentialthrough protonation of the coordinated complex or by the hydroxideacting as a ligand. The equilibrium potential for the formaldehydeoxidation becomes more negative with increasing pH. The use of acomplexing agent in the bath is essential because it prevents theprecipitation of the copper hydroxide under alkaline solutions. Theethylenediaminetetraacetic acid based electroless copper solution has arelatively low deposition rate, with a high bath stability, because ofthe strength of the complex with cupric ions (which is why it is usedprimarily in the PCB industry). The past challenge with triethanolamineis that it can conflict with the oxidation of formaldehyde and theninhibit the initial copper deposition on the active coordinationcomplexes/catalysts. The triethanolamine based electroless coppersolution achieves a higher deposition rate then theethylenediaminetetraacetic acid based solution, however with the high pH(for acceleration of the deposition rate), it will remove or impair thecoordinated complex/catalyst from being built upon by the cupric ions.Therefore, combining the complexing agent solutions can mitigate thestability issues, or by sealing the coordination complex/catalyst withcopper, which will allow the accelerated electroless copper build up,either will overcome the challenge of the triethanolamine basedelectroless copper solution. In the case of the combination ofcomplexing agents, the deposition rate increases as the mole ratio oftriethanolamine to ethylenediaminetetraacetic acid increases and thebath stability is maintained. Any uneven deposition of copper on theactivated surface can be enhanced by adjusting the operating temperatureand pH of the bath. The net rate of deposition of the high speedelectroless copper plating occurs at the mixed potential when thecathodic and anodic currents are equal.

Experimental Parameters:

Target pH of solutions should be in the range of 11 to 13 using NaOH orH2SO4

Target temperature range should be 45° to 70° C. (preferably 55° C.)

Strong Nitrogen Agitation

Ratio of components: 1 part copper (0.04M cupric sulfate), 3 partsreducing agent (0.12M formaldehyde), and 5 parts complexing agent(s)(0.20M ethylenediaminetetraacetic acid and triethanolamine mix) Note:All solutions to be prepared with analytical grade reagents anddeionized water.

Use a 5 minute dip of the solution consisting of the Shipley Cuposit 328material as follows: 328 A 12.5% by volume, 328 L 12.5% by volume, 328 C2.5% by volume, H2O (De-Ionized) 72.5% by volume, as the sealant to theaggressive pH in the triethanolamine solution prior to the high speedcopper electroless tank.

The reduction performance of cupric ions in alkaline solutions dependson the characteristics of the complexing agents utilized. This isbecause of the different complexing abilities as evidenced by theirformation constants with cupric ions. Without the protective sealantstep after the initiation of the coordinated complex/catalyst,aggressive deposition would be problematic, however with the institutionof this step then the deposition rate can approach 20μ per hour (withincreased temperature and pH). By combining the complexing agents tomake up an aggregate complexing agent with a mixed potential, theoxidation of the reducing agent is still independent of the complexingagents but can be accelerated by increasing pH of the bath.Ethylenediaminetetraacetic acid and sodium potassium tartrate, both havea high formation constant with cupric ions, and therefore a complexingagent based electroless copper process has a lower deposition rate andbetter bath stability with either of these complexing agents. Thecomplexing ability of triethanolamine or triisopropanolamine is muchlower than that of ethylenediaminetetraacetic acid and sodium potassiumtartrate, and also could be detrimental to the coordinationcomplex/catalyst activation of the substrate surface, unless the processstep of using a protective layer over the coordination complex/catalystprecedes the high speed electroless bath. With the different testing ofthe potential combinations of complexing agents and reducing agents bythe above mentioned ratios, it is clear that the deposition rateincreased with the mole ratio between the aggressive complexing agentsand the complexing agents that promote stability. The surface coverageand speed of deposition was also adjusted by the operating temperatureand pH of the bath (as it increased).

In at least one embodiment, depositing a conductive material onto thesubstrate surface comprises deposition of a non-metallic conductivesubstance onto the portion of the substrate surface, or the image thatencompassed or comprising the reduced metal coordination complex. In atleast one embodiment, the non-metallic conductive material is depositedonto the portion of the surface comprising the reduced metalcoordination complex by electrostatic dispersion. In at least oneembodiment, the entire non-conductive substrate surface is activated andthe metal coordination complex is deposited onto the entire surface. Inat least one embodiment, the entire non-conductive substrate surface isactivated and the metal coordination complex is deposited on a part ofthe activated surface.

The enablements described in detail above are considered novel over theprior art of record and are considered critical to the operation of atleast one aspect of the invention and to the achievement of the abovedescribed objectives. The words used in this specification to describethe instant embodiments are to be understood not only in the sense oftheir commonly defined meanings, but to include by special definition inthis specification: structure, material or acts beyond the scope of thecommonly defined meanings Thus if an element can be understood in thecontext of this specification as including more than one meaning, thenits use must be understood as being generic to all possible meaningssupported by the specification and by the word or words describing theelement.

The definitions of the words or drawing elements described herein aremeant to include not only the combination of elements which areliterally set forth, but all equivalent structure, material or acts forperforming substantially the same function in substantially the same wayto obtain substantially the same result. In this sense it is thereforecontemplated that an equivalent substitution of two or more elements maybe made for any one of the elements described and its variousembodiments or that a single element may be substituted for two or moreelements in a claim.

As used herein, any term of approximation means that the word or phrasemodified by the term of approximation need not be exactly that which iswritten but may vary from that written description to some extent. Theextent to which the description may vary will depend on how great achange can be instituted and have one of ordinary skill in the artrecognize the modified version as still having the desired properties,characteristics and capabilities of the word or phrase unmodified by theterm of approximation. In general, but with the preceding discussion inmind, a numerical value herein that is modified by a word ofapproximation may vary from the stated value by plus-or-minus 10% unlessexpressly stated otherwise.

Changes from the claimed subject matter as viewed by a person withordinary skill in the art, now known or later devised, are expresslycontemplated as being equivalents within the scope intended and itsvarious embodiments. Therefore, obvious substitutions now or later knownto one with ordinary skill in the art are defined to be within the scopeof the defined elements. This disclosure is thus meant to be understoodto include what is specifically illustrated and described above, what isconceptually equivalent, what can be obviously substituted, and alsowhat incorporates the essential ideas.

The scope of this description is to be interpreted only in conjunctionwith the appended claims and it is made clear, here, that the namedinventor believes that the claimed subject matter is what is intended tobe patented.

What is claimed is:
 1. A method of conductive image using high speedelectroless plating comprising the steps of: preparing the surface of asubstrate, the substrate surface having a thickness; depositing a metalcoordination complex within the surface of the substrate; reducing themetal coordination complex to form a metal image in the surface of thesubstrate; depositing a protective material onto the metal image; andelectrolessly plating metal onto the metal image.